The corticoids are a particular type of steroid having the basic carbon skeletal formula I which contains 21 carbon atoms in 4 rings, A thru D.
The A-D rings of the steroid nucleus being relatively planar will have some groups which are positioned above (.beta.) the plane of cyclopentenophenanthrene nucleus and are designated by and others which are positioned below (.alpha.) the plane and are designated by . Further, .about. indicates the substituent is either positioned in the .alpha. or in the .beta. position to the plane of the ring.
A well known example of the corticoids is dexamethasone, a glucocorticoid which is represented by the formula II.
The pharmaceutical utility of the corticoids is well known to those skilled in the art. They are used for relief of inflammatory manifestations, endocrine disorders, adrenocortical insufficiency, rheumatic disorders, dermatologic diseases, allergic states, ophthalmic diseases, respiratory diseases, hematologic disorders, neoplastic diseases, edematous states, etc.
The corticoids are administered orally, topically or parenterally in dosages which are well known to those skilled in the art.
A preparation of corticoid-type compounds of the similar scope as the present invention is disclosed in U.S. Pat. No. 4,041,055. The preparation makes use of a sulfenate-sulfoxide rearrangement to define the stereochemistry of corticosteroids at C-17. The rearrangement is also discussed by VanRheenen, et al., in the "New Synthesis of Corticosteroids from 17-Keto Steroids: Application and Stereochemical Study of the Unsaturated Sulfoxide-Sulfenate Rearrangement," J. Org. Chem., Communications, vol. 44, no. 9, pp. 1582-4 (1979). More recently each of the following references discusses processes related to the corticoid groups at the 17 position of the steroidal ring: Redpath, et al., "Stereoselective Synthesis of Steroid Side-Chains", Chemical Society Reviews, vol. 12, no. 1, pp. 75-98 (1983); Morera, et al., "Preparative and Stereochemical Features of the Sulfoxide-Sulfenate [2,3] Sigmatropic Rearrangement in 17-Vinyl-17-Hydroxy Steroids", J. of Org. Chem., vol. 48, no. 1, pp. 119-21 (1983); Daniewski, et al. " Synthesis of the Corticoid Side-Chain", J. of Org. Chem., vol. 47, no. 15, pp. 2993-5 (1982); and Barton, et al., "Efficient Synthesis of the Corticosteroid Side-Chain from 17-Ketones", J. of the Chem. Soc. Chemical Communications, no. 15, pp. 774-5, 1981. However, none of the above teachings appreciates the preparation of 17-.alpha.-hydroxyprogesterones of the present invention from steroidal-type compounds having a double bond from the 16 to 17 carbon in the D ring. The invention includes selected desireable variations of double bonds and substituents on rings A-C.